CN106981500A - The solar cell and LED of all-perovskite show integrated system and preparation method thereof - Google Patents

The solar cell and LED of all-perovskite show integrated system and preparation method thereof Download PDF

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CN106981500A
CN106981500A CN201710082403.9A CN201710082403A CN106981500A CN 106981500 A CN106981500 A CN 106981500A CN 201710082403 A CN201710082403 A CN 201710082403A CN 106981500 A CN106981500 A CN 106981500A
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perovskite
solar cell
substrate
film
layer
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崔四维
刘风采
焦钰清
黄霏
王浩然
倪超伟
蔡江
张新月
徐闰
杨绪勇
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University of Shanghai for Science and Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/60—OLEDs integrated with inorganic light-sensitive elements, e.g. with inorganic solar cells or inorganic photodiodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

Integrated system and preparation method thereof is shown the invention discloses a kind of solar cell of all-perovskite and LED, using single step solution growth MAPbI3‑xClxFilm, pass through wire, the anode of the solar cell of perovskite is connected with the negative electrode of light-emitting diode display part, and the cathode substrate of the solar cell of perovskite and the anode substrate of light-emitting diode display part are connected, closed-loop path is formed, solar cell absorbs solar energy, and it is that light-emitting diode display part is powered to release electric energy, completes the preparation of solar cell and the integrated spin coating of light-emitting diode display part, accomplishes all-perovskite system, raw material are relative to be easy to get, and saving raw material and production process more has economic benefits.The present invention prepares efficient perovskite solar cell and light-emitting diode display respectively, finally enters row set, and process is simple, is easy to streamline to prepare, and saves material, and time saving province can, it is easy to mass produces.

Description

The solar cell and LED of all-perovskite show integrated system and preparation method thereof
Technical field
The present invention relates to a kind of LED display system and preparation method thereof, more particularly to a kind of solar cell and LED show Show integrated system and preparation method thereof, applied to photoelectric device preparing technical field.
Background technology
Increasingly sharpening for ring is broken with environment as global energy is consumed, traditional fossil energy is difficult to meet human economic society The need for sustainable development.Therefore, people always search for cleaning, the reproducible energy.There are a variety of new energy continuous at present It is utilized exploitation, such as solar energy, water energy, wind energy.Wherein solar energy is due to its innumerable and stability of originating, as most There is the renewable new energy of development potentiality.How effectively, people are enjoyed to pay close attention to always at low cost using solar energy.Currently with The formula of solar energy mainly has two kinds：Photothermal deformation and opto-electronic conversion.Photothermal conversion has been widely used, its topmost representative It is exactly solar water heater；And photoelectric conversion is then the high speed development stage that is in, its best mode is exactly solar cell, again Referred to as photovoltaic cell.Solar cell pollution-free, zero-emission, does not produce any noise and radiation during photoelectric conversion, is A kind of excellent reforming unit of environment-friendly green energy resource.
Traditional silicon solar cell is occupied an leading position because efficiency is close to 20% in photovoltaic market.But monocrystalline silicon The problems such as time consumption and energy consumption, cost height, complex manufacturing, production process can cause environmental pollution, limit it makes on a large scale With.Although second generation solar cell saves material, growth cost is low, also there is unavoidable shortcoming, Te, In, Ga etc. All it is the seldom element of reserves on the earth, more rare than Au, this will be such that it does not mass produce, its production of strong influence Value.Third generation solar cell, such as organic photovoltaic (OPVs), DSSC (DSCs) and quantum dot solar Battery (QDSCs), is that, by blade coating, the technique such as Shiscreen printings and spraying is coated in unconventional substrate to protect by solution Low-cost solar cell power generation is demonstrate,proved, but it is relatively unstable.Therefore, exploitation high-photoelectric transformation efficiency, low cost it is new too Positive energy battery turns into emphasis of concern.In recent years, a kind of perovskite sun for making light absorbent with metal organohalogen compounds Energy battery is due to one of its high-photoelectric transformation efficiency, focus that is inexpensive and being studied as photovoltaic art.
Traditional non-crystal silicon solar cell, by development for many years, its photoelectric transformation efficiency Slow lifting compares it Under, the novel solar battery occurred in recent years such as organic solar batteries (OPV), perovskite solar cell, dye sensitization Solar cell (DSSC) and quantum dot solar cell (quantum dot solar cell), development are very fast, opto-electronic conversion The obvious of improved efficiency is in all kinds of novel solar batteries, and the photoelectric transformation efficiency development of perovskite solar cell is the most fast Speed, laboratory research efficiency is not defeated in traditional silicon solar cell more than 20%.
Perovskite makes people start thinking in the success of area of solar cell, and can it as a kind of luminescent material.The U.S. Researcher has found that perovskite can realize high-brightness LED with lower cost and simpler technique.Calcium for making LED Titanium ore is referred to as organic metal halogenation perovskite, is the mixture being made up of lead, carbon-based ion and halogen ion.This material can It is dissolved in well among usual vehicle, and the cost needed for aggregating into perovskite crystal, whole process after the drying is very low, work Skill also very simple.Britain research personnel have confirmed that the application of perovskite material newly, that is, are used to manufacture highlighted The LED of degree, the result of study is published on nature and nanometer technology magazine.First LED commercial applications based on perovskite It is expected to realize before 2019.
Main focus has the CH of hybrid inorganic-organic at present3NH3PbX3With the CsPbX of full-inorganic3.Preparation method has, rotation Coating, anion exchange method, solution deposition method etc..
Perovskite LED in 2016 has many breakthrough progress, particularly 2D perovskites LED.Current PeLED brightness note Record is 21014cd/m2.In terms of efficiency, end of last year EQE reaches more than 8% for the first time, and at least two 2DPeLED in this year EQE reached more than 8%, but preparation technology is complicated, and commercial applications difficulty is higher.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind The solar cell and LED of all-perovskite show integrated system and preparation method thereof, using single step solution growth MAPbI3- xClxFilm, and solar cell and perovskite LED display are prepared, and perovskite solar cell and perovskite LED are carried out Integrated, the solar cell and LED for forming all-perovskite show integrated system, and system architecture is compact, and integrated level is high, process letter It is single, it is easy to streamline to prepare, and material is saved, time saving province can, it is easy to mass produces.
To reach that foregoing invention creates purpose, the present invention uses following technical proposals：
The solar cell and LED of a kind of all-perovskite show integrated system, by solar cell and light-emitting diode display part group Dress forms integrated system, and solar cell is the solar cell device using plane perovskite thin film, and light-emitting diode display part is adopted With perovskite thin film as luminous material layer, by wire, by the anode of the solar cell of perovskite and light-emitting diode display part Negative electrode is connected, and the cathode substrate of the solar cell of perovskite and the anode substrate of light-emitting diode display part are connected, and forms closure Loop, solar cell absorbs solar energy, and it is that light-emitting diode display part is powered to release electric energy.
As currently preferred technical scheme, solar cell is successively by anode substrate, titanium dioxide Window layer, calcium titanium Ore deposit film layer, hole transport layer film and cathode electrode composition plane perovskite solar cell device.
As the further preferred technical scheme of such scheme, perovskite thin film is MAPbI3-xClxPerovskite thin film, Wherein A is positive monovalence organic molecule group.
As the further preferred technical scheme of such scheme, light-emitting diode display part is successively by cathode substrate, ZnO film Electron transfer layer, the luminescent layer of perovskite thin film, CBP films hole transmission layer, MoO3Film hole injection layer and anode.In calcium Hole blocking layer is also preferably provided between the luminescent layer and CBP film hole transmission layers of titanium ore film.It is preferred that luminescent layer is MAPbI3-xClxPerovskite thin film, wherein A are positive monovalence organic molecule groups.
It is used as the further preferred technical scheme of such scheme of the present invention, preferably MAPbI3-xClxPerovskite thin film is CH3NH3PbI3-xClxFilm.
The solar cell and LED of a kind of all-perovskite show the preparation method of integrated system, comprise the following steps：
A. the preparation of perovskite solar cell：
Transparent conducting glass substrate is cut, corroded and cleaned by I：
Transparent conducting glass substrate is cut into the fritter substrate of the shape and size with setting, then with zinc powder and rubbing Your concentration is not less than the width that 2M HCl solution erodes conductive layer setting on fritter substrate surface, then with rubbing for having diluted Your concentration for 2mol/L HF acid soak fritter substrates the region at least 60 seconds of being corroded, to ensure the area that is corroded of fritter substrate The FTO layers corrosion in domain is clean, completes the patterned process to fritter substrate, then carries out that Qula is logical to wash by rubbing with the hands successively, then spend from Sub- water is rinsed, and is then carried out ultrasound using acetone or is cleaned by ultrasonic using ethanol, then preserves clean fritter substrate It is standby in ethanol；
The preparation of II window layer material titanium dioxide：
Molar concentration is not less than to 2M TiO2Precursor solution, be spin-coated under not higher than 2500rpm rotating speed by On the fritter substrate that the corrosion cleaning of step I is finished, TiO then will be coated2The fritter substrate of precursor solution carries out burned solidification At least 10min, makes solidification on fritter substrate combine TiO2Material layer, then will carry TiO2The fritter substrate of material layer is transferred to In Muffle furnace, in air atmosphere be not less than 500 DEG C anneal at least 30 minutes, titanium dioxide Window layer is prepared, then to two The surface of titanium oxide Window layer carries out TiCl4Processing, is caused in titanium dioxide window layer surface formation titanium dioxide one layer tiny Close crystal grain, as progress TiCl4During processing, first by TiCl4It is placed in refrigerator and is cooled to not higher than 4 DEG C, then in the bar being stirred continuously Under part, a certain amount of TiCl is added dropwise into the deionized water in ice bath environment4, configuration concentration is not higher than 0.04mol/L TiCl4The aqueous solution, is then placed in TiCl by the substrate with titanium dioxide Window layer of preparation4In the aqueous solution, it is heated to not low Keep being no less than 30min in 70 DEG C, the substrate with titanium dioxide Window layer is then cleaned into drying, it is standby；
III single steps solution growth prepares CH3NH3PbI3-xClxPerovskite thin film：
Using spin-coating method by CH3NH3PbI3-xClxTwo kinds of precursor solutions be coated uniformly on what is prepared in step II respectively In the titanium dioxide Window layer combined with substrate, calcium titanium ore bed is prepared, spin coating rotating speed is 1500~3000rpm, and spin-coating time is extremely It is less 60 seconds, it is after spin coating, wet calcium titanium ore bed is directly burned at a temperature of not higher than 100 DEG C at least 90 minutes, make calcium titanium The color of ore bed is all changed into sepia from yellow, and then the substrate with calcium titanium ore bed is dried at ambient temperature, Annealed again, that is, obtain the CH of grey black3NH3PbI3-xClxFilm；
The preparation of IV hole transport layer materials：
0.2292g spiro-MeOTAD powder is added in 1 milliliter of chlorobenzene, stirs at normal temperatures, treats that powder is completely molten 34 microlitres of 4- tert .-butylpyridines are added dropwise after solution, 0.1011g lithium salts are added in 500 microlitres of acetonitriles, stirring at normal temperature dissolves it, Take 100 microlitres of this uniform liquid dissolved to be added in spiro-MeOTAD precursor solutions, continue to stir equal to solution It is even, that is, the precursor solution that mass percent concentration is 16% is prepared, chlorobenzene is then added and this solution is diluted to original concentration 1/3rd, be needed for hole transmission layer HTM precursor solutions, will before this then to be not less than 2000rpm rotating speed Drive liquid solution to be spun on the calcium titanium ore bed prepared in step III, you can obtain hole transport layer film, then condition of nitrogen gas Under, shading stands at least 24h；
V plated electrodes：
After the device shading prepared in step IV is stood, 10 are not higher than in body vacuum-4Under conditions of Torr, pass through Vacuum evaporation technology, the gold that evaporation thickness is not higher than 200nm on hole transport layer film prepares to electrode and completes plane Type perovskite solar cell device；
B. the preparation of perovskite light-emitting diode display part：
(1) the preparation of ZnO nano particle：ZnO nano particle is synthesized using sol-gel process, comprised the following steps that：
1. 3mmol zinc acetate dihydrate is dissolved in 30mlDMSO solution；
2. 5mmol TMAH is dissolved in 30ml ethanol, and be added dropwise 1. with the speed for being not less than 8ml/min with syringe pump In resulting solution, react lasting at room temperature and carry out being no less than 1h；
3. excessive toluene cleaning is added, and centrifugation separates out ZnO nano particle, and be dispersed in ethanol solution, obtain To zinc oxide ethanol solution, electron transport layer materials are used as spin coating；
(2) perovskite is synthesized：
By 1mmol MAI and 1mmol PbI2DMSO or mass fraction are dissolved in in 40wt.% DMF, in nitrogen ring Border, heats and stirs at least 2 hours at not higher than 60 DEG C, obtain MAPbI3Solution；
(3) the preparation of Pe-LED devices：
(a) glass substrate is first washed by rubbing with the hands with cleanser, it is then clear with liquid detergent, deionized water, acetone, isopropanol ultrasound respectively Wash each at least 30 minutes, then glass substrate is toasted at least 10 minutes, cathode substrate is used as；
(b) cathode substrate prepared in step (a) is transferred in glove box, the atmosphere in control glove box makes O2 Concentration is not higher than 1PPM, and H2The concentration of O steam is also not higher than 1PPM, by the step (1) zinc oxide ethanol solution of middle preparation Concentration is adjusted to 25mg/ml, then by 25mg/ml zinc oxide ethanol solution to be not less than 2000rpm rotating speed spin coating at least Annealed at least 30 minutes in cathode substrate, and in nitrogen atmosphere with being not less than 150 DEG C within 60 seconds, then naturally cool to room Temperature, i.e., prepare ZnO film in cathode substrate, is used as electron transfer layer；
(c) using the MAPbI prepared in step (2)3, will on solution, the ZnO film surface prepared in step (b) MAPbI3Solution is annealed at least with being not less than 3000rpm rotating speed spin coating 40~60 seconds with the temperature for being not less than 80 DEG C 10 minutes, i.e., MAPbI is prepared on ZnO film3Film, as luminescent layer, then with speckling with the swab stick of DMF solution by negative electrode The unnecessary ZnO film of substrate surrounding, MAPbI3Film is wiped, and so that the electrode for exposing cathode substrate draws angle, is obtained after finishing Substrate device；
(d) with not higher thanSpeed, evaporation thickness is not higher than what 60nm CBP materials were prepared in step (c) MAPbI3On film, CBP films are prepared, hole transmission layer is used as；Then with not higher thanSpeed, CBP films it On, evaporation thickness is not higher than 10nm MoO3Material layer, prepares MoO3Film, is used as hole injection layer；
(e) electrode is steamed：Under vacuum conditions, the MoO prepared in step (d)3On film, to be not less thanSpeed Degree evaporation thickness is not higher than 150nm Al electrodes, completes the preparation of light-emitting diode display part；
C. system is integrated：
By wire, prepare the anode of the perovskite solar cell device prepared in step a and in stepb The negative electrode series connection of light-emitting diode display part, and the anode of the cathode substrate of perovskite solar cell device and light-emitting diode display part is served as a contrast Bottom is connected, and forms closed-loop path, perovskite solar cell device absorbs solar energy, and it is the confession of light-emitting diode display part to release electric energy Electricity, the solar cell and LED for obtaining all-perovskite shows integrated system.
As the further preferred technical scheme of such scheme of the present invention, when preparing light-emitting diode display part in stepb, Step (3) the step of (c) prepare MAPbI3After film, the substrate device prepared in step (c) is then transferred to multi-source gas In phase depositing system, the chamber pressure for controlling multi-source gas-phase deposition system is 5x10-3Pa, the temperature of regulation correspondence evaporation source, makes TPBI materials reach sublimation point, and with gaseous deposit in MAPbI3On film, densification TPBI films are formed, hole barrier is used as Layer, then in step (d), on the TPBI films that evaporation CBP materials are prepared in step (c), prepares CBP films, as Hole transmission layer.
The present invention compared with prior art, substantive distinguishing features and remarkable advantage is obviously protruded with following：
1. the perovskite thin film that the present invention is prepared using single step flash method in situ, energy consumption is low, evaporation rate is fast, and the time is short, Film is without cavity and large area is uniform, and substrate range of choice is wide, is adapted to do planar device；
2. the present invention uses MAPbI3The preparation that solar cell and LED are shown is completed, accomplishes all-perovskite system, former material Material is relative to be easy to get, and saving raw material and production process more has economic benefits；
3. the present invention prepares efficient perovskite solar cell and light-emitting diode display respectively, finally enter row set, process Simply, it is easy to streamline to prepare, and saves material, time saving province can, it is easy to mass produces.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that the embodiment of the present invention one prepares perovskite solar cell using solwution method.
Fig. 2 is the schematic flow sheet that the embodiment of the present invention one prepares perovskite light-emitting diode display.
Fig. 3 shows the structure principle chart of integrated system for the solar cell and LED of the all-perovskite of the embodiment of the present invention one.
Fig. 4 shows the appearance assumption diagram of integrated system for the solar cell and LED of the all-perovskite of the embodiment of the present invention one.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 3 and Fig. 4, the solar cell and LED of a kind of all-perovskite show integrated system, It is characterized in that:Integrated system is formed by solar cell 1 and the assembling of light-emitting diode display part 2, solar cell 1 is to use plane The solar cell device of type perovskite thin film, light-emitting diode display part 2 uses perovskite thin film as luminous material layer, by leading Line, the anode of the solar cell 1 of perovskite is connected with the negative electrode of light-emitting diode display part 2, and by the solar cell of perovskite 1 cathode substrate and the anode substrate series connection of light-emitting diode display part 2, form closed-loop path, and solar cell 1 absorbs solar energy, and It is that light-emitting diode display part 2 is powered to release electric energy.
In the present embodiment, referring to Fig. 3, solar cell 1 is successively by anode substrate, titanium dioxide Window layer, perovskite Film layer, hole transport layer film and cathode electrode composition plane perovskite solar cell device.Perovskite thin film is MAPbI3-xClxPerovskite thin film, wherein A are positive monovalence organic molecule groups.
In the present embodiment, referring to Fig. 3, light-emitting diode display part 2 is successively by cathode substrate, ZnO film electron transfer layer, calcium Luminescent layer, CBP films hole transmission layer, the MoO of titanium ore film3Film hole injection layer and anode.Luminescent layer is MAPbI3-xClx Perovskite thin film, wherein A are positive monovalence organic molecule groups.MAPbI3-xClxPerovskite thin film is CH3NH3PbI3-xClxIt is thin Film.
In the present embodiment, referring to Fig. 1~4, the solar cell and LED of a kind of all-perovskite show the system of integrated system Preparation Method, comprises the following steps：
A. the preparation of perovskite solar cell：
Transparent conducting glass substrate is cut, corroded and cleaned by I：
Take commercially available FTO electro-conductive glass some, the square small of about 19.5 × 19.5mm is cut into using glass cutting machine Block, FTO Conducting Glass is cut into the fritter substrate of the shape and size with setting, then with zinc powder and molar concentration The width of conductive layer setting is eroded on fritter substrate surface for 2M HCl solution, then is with the molar concentration diluted The region 60 seconds of being corroded of 2mol/L HF acid soak fritter substrates, to ensure that the FTO layers in the region that is corroded of fritter substrate are rotten Erosion is clean, completes the patterned process to fritter substrate, then carries out that Qula is logical to wash by rubbing with the hands successively, then with deionized water rinsing, so Ultrasound is carried out using acetone afterwards or is cleaned by ultrasonic using ethanol, clean fritter substrate is then preserved standby in ethanol With；
The preparation of II window layer material titanium dioxide：
By the TiO that molar concentration is 2M2Precursor solution, is spin-coated on clear by the corrosion of step I under 2500rpm rotating speed Wash on complete FTO fritter substrate, then will coat TiO2The fritter substrate of precursor solution carries out burned solidification 10min, Solidification on fritter substrate is set to combine TiO2Material layer, then will carry TiO2The fritter substrate of material layer is transferred in Muffle furnace, Under air atmosphere, and annealed 30 minutes at 500 DEG C, titanium dioxide Window layer is prepared, then to the surface of titanium dioxide Window layer Carry out TiCl4Processing, in titanium dioxide window layer surface formation titanium dioxide dense crystal grain one layer tiny, as progress TiCl4Place During reason, first by TiCl4It is placed in refrigerator and is cooled to 4 DEG C, then under conditions of being stirred continuously, to goes in ice bath environment A certain amount of TiCl is added dropwise in ionized water4, configuration concentration is 0.04mol/L TiCl4The aqueous solution, then carrying preparation The substrate of titanium dioxide Window layer is placed in TiCl4In the aqueous solution, 70 DEG C of holding 30min are heated to, titanium dioxide then will be carried The substrate of Window layer cleans drying, standby；TiCl4Easily occurs hydrolysis with the water in air at normal temperatures, to be clarified TiCl4The aqueous solution, it is necessary to suppress TiCl as far as possible4Hydrolysis rate；
III single steps solution growth prepares CH3NH3PbI3-xClxPerovskite thin film：
Spin-coating method is used by CH using liquid-transfering gun3NH3PbI3-xClxTwo kinds of mass concentrations be 40wt% precursor solution It is coated uniformly on respectively in the titanium dioxide Window layer combined with substrate prepared in step II, prepares calcium titanium ore bed, spin coating turns Speed is 3000rpm, and spin-coating time is 60 seconds, after spin coating, and wet calcium titanium ore bed is directly burned at a temperature of 100 DEG C 90 points Clock, makes the color of calcium titanium ore bed all be changed into sepia from yellow, then by the substrate with calcium titanium ore bed at ambient temperature It is dried, then is annealed, that is, obtains the CH of grey black3NH3PbI3-xClxFilm；
The preparation of IV hole transport layer materials：
0.2292g spiro-MeOTAD powder is added in 1 milliliter of chlorobenzene, stirs at normal temperatures, treats that powder is completely molten 34 microlitres of 4- tert .-butylpyridines are added dropwise after solution, 0.1011g lithium salts are added in 500 microlitres of acetonitriles, stirring at normal temperature dissolves it, Take 100 microlitres of this uniform liquid dissolved to be added in spiro-MeOTAD precursor solutions, continue to stir equal to solution It is even, that is, the precursor solution that mass percent concentration is 16% is prepared, chlorobenzene is then added and this solution is diluted to original concentration 1/3rd, be needed for hole transmission layer HTM precursor solutions, then with 2000rpm rotating speed spin coating 60s, by this Precursor solution is spun on the calcium titanium ore bed prepared in step III, you can obtain hole transport layer film, then nitrogen bar Under part, shading stands 24h；
V plated electrodes：
After the device shading prepared in step IV is stood, in body vacuum 10-4Under conditions of Torr, steamed by vacuum Hair technique, evaporation thickness is the golden to electrode of 200nm on hole transport layer film, that is, prepares and complete plane perovskite too Positive energy battery device；
B. the preparation of perovskite light-emitting diode display part：
(1) the preparation of ZnO nano particle：ZnO nano particle is synthesized using sol-gel process, comprised the following steps that：
1. 3mmol zinc acetate dihydrate is dissolved in 30mlDMSO solution；
2. 5mmol TMAH is dissolved in 30ml ethanol, and it is molten with syringe pump with 8ml/min speed 1. gained to be added dropwise In liquid, react persistently carry out 1h at room temperature；
3. excessive toluene cleaning is added, and centrifugation separates out ZnO nano particle, and be dispersed in ethanol solution, obtain To zinc oxide ethanol solution, electron transport layer materials are used as spin coating；
(2) perovskite is synthesized：
By 1mmol MAI and 1mmol PbI2DMSO or mass fraction are dissolved in in 40wt.% DMF, in nitrogen ring Border, heats and stirs 2 hours at 60 DEG C, obtain MAPbI3Solution；
(3) the preparation of Pe-LED devices：
(a) first wash ito glass substrate by rubbing with the hands with cleanser, then surpassed respectively with liquid detergent, deionized water, acetone, isopropanol Sound is cleaned each 30 minutes, is then toasted ito glass substrate 10 minutes, is used as cathode substrate；
(b) cathode substrate prepared in step (a) is transferred in glove box, the atmosphere in control glove box makes O2 Concentration is 1PPM, and H2The concentration of O steam is 1PPM, will be adjusted in the concentration of the step (1) zinc oxide ethanol solution of middle preparation 25mg/ml, then by 25mg/ml zinc oxide ethanol solution with 2000rpm rotating speed spin coating 60 seconds in cathode substrate, and Annealed 30 minutes with 150 DEG C in nitrogen atmosphere, annealing can accelerate solvent to volatilize and form fine and close lattice, then naturally cool to room Temperature, i.e., prepare ZnO film in cathode substrate, is used as electron transfer layer；
(c) using the MAPbI prepared in step (2)3, will on solution, the ZnO film surface prepared in step (b) MAPbI3Solution carries out annealing 10 minutes with 3000rpm rotating speed spin coating 60 seconds with 80 DEG C of temperature, solid by solid-gas- Three-phase conversion process, i.e., be prepared for MAPbI on ZnO film3Film, as luminescent layer, then with the cotton for speckling with DMF solution Rod is by the unnecessary ZnO film of cathode substrate surrounding, MAPbI3Film is wiped, and so that the electrode for exposing cathode substrate draws angle, is obtained Substrate device after finishing；
(d) withSpeed, the MAPbI that evaporation thickness is prepared in the step (c) for 60nm CBP materials3Film it On, CBP films are prepared, hole transmission layer is used as；Then withSpeed, on CBP films, evaporation thickness be 10nm MoO3Material layer, prepares MoO3Film, is used as hole injection layer；
(e) electrode is steamed：Under vacuum conditions, the MoO prepared in step (d)3On film, withSpeed evaporation Thickness is 150nm Al electrodes, completes the preparation of light-emitting diode display part；
C. system is integrated：
By wire, prepare the anode of the perovskite solar cell device prepared in step a and in stepb The negative electrode series connection of light-emitting diode display part, and the anode of the cathode substrate of perovskite solar cell device and light-emitting diode display part is served as a contrast Bottom is connected, and forms closed-loop path, perovskite solar cell device absorbs solar energy, and it is the confession of light-emitting diode display part to release electric energy Electricity, the solar cell and LED for obtaining all-perovskite shows integrated system.
The present embodiment utilizes single step solution growth MAPbI3Film and its solar cell and perovskite LED display, The perovskite solar cell for having prepared completion is connected by evaporating wire, and passes through plain conductor and LED batteries It is connected, the present embodiment uses MAPbI3The preparation that solar cell and LED are shown is completed, accomplishes all-perovskite system, former material Material is relative to be easy to get, and saving raw material and production process more has economic benefits；The present embodiment prepares efficient calcium titanium respectively Ore deposit solar cell and light-emitting diode display, finally enter row set, and process is simple, is easy to streamline to prepare, and save material, save Shi Shengneng, it is easy to mass produce.
Experimental test and analysis：
An all-perovskite solar cell is made in embodiment one and LED shows integrated system, can reach as shown in Figure 4 Display effect.The perovskite thin film that embodiment one is prepared using single step flash method in situ, energy consumption is low, and evaporation rate is fast, and the time is short, Film is without cavity and large area is uniform, and substrate range of choice is wide, is adapted to do planar device.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, in solar cell and LED the display integrated system of all-perovskite, in perovskite thin film Hole blocking layer is also set up between luminescent layer and CBP film hole transmission layers.
In the present embodiment, prepared in the step b for preparing the solar cell of all-perovskite and LED display integrated systems During light-emitting diode display part, and step (3) the step of (c) prepare MAPbI3After film, the substrate that will be then prepared in step (c) Device is transferred in multi-source gas-phase deposition system, and the chamber pressure for controlling multi-source gas-phase deposition system is 5x10-3Pa, regulation pair The temperature of evaporation source is answered, TPBI materials is reached sublimation point, and with gaseous deposit in MAPbI3On film, densification TPBI is formed Film, as hole blocking layer, then in step (d), on the TPBI films that evaporation CBP materials are prepared in step (c), CBP films are prepared, hole transmission layer is used as.The present embodiment includes hole blocking layer in the light-emitting diode display part of preparation, can significantly carry The performance of the luminous efficiency of high light-emitting diode display part, further optimization light-emitting diode display part.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with Made according to the purpose of the innovation and creation of the present invention under a variety of changes, all Spirit Essence and principle according to technical solution of the present invention Change, modification, replacement, the combination or simplified made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, Solar cell without departing from all-perovskite of the present invention and LED show integrated system and preparation method thereof technical principle and Inventive concept, belongs to protection scope of the present invention.

Claims (9)

1. the solar cell and LED of a kind of all-perovskite show integrated system, it is characterised in that:By solar cell (1) and Light-emitting diode display part (2) assembling forms integrated system, and the solar cell (1) is the sun using plane perovskite thin film Energy battery device, the light-emitting diode display part (2) uses perovskite thin film as luminous material layer, by wire, by perovskite The anode of solar cell (1) is connected with the negative electrode of light-emitting diode display part (2), and by the negative electrode of the solar cell (1) of perovskite The anode substrate series connection of substrate and the light-emitting diode display part (2), forms closed-loop path, and the solar cell (1) absorbs the sun Can, and it is light-emitting diode display part (2) power supply to release electric energy.
2. the solar cell of all-perovskite and LED show integrated system according to claim 1, it is characterised in that：It is described Solar cell (1) is successively by anode substrate, titanium dioxide Window layer, perovskite thin film layer, hole transport layer film and negative electrode Electrode constitutes plane perovskite solar cell device.
3. the solar cell of all-perovskite and LED show integrated system according to claim 2, it is characterised in that：It is described Perovskite thin film is MAPbI3-xClxPerovskite thin film, wherein A are positive monovalence organic molecule groups.
4. the solar cell of all-perovskite and LED show integrated system according to claim 1, it is characterised in that：It is described Light-emitting diode display part (2) is successively by cathode substrate, ZnO film electron transfer layer, the luminescent layer of perovskite thin film, CBP films hole Transport layer, MoO3Film hole injection layer and anode.
5. the solar cell of all-perovskite and LED show integrated system according to claim 4, it is characterised in that：In calcium Hole blocking layer is also set up between the luminescent layer and CBP film hole transmission layers of titanium ore film.
6. the solar cell of all-perovskite and LED show integrated system according to claim 4, it is characterised in that：It is described Luminescent layer is MAPbI3-xClxPerovskite thin film, wherein A are positive monovalence organic molecule groups.
7. the solar cell of all-perovskite and LED show integrated system according to claim 3 or 6, it is characterised in that：Institute State MAPbI3-xClxPerovskite thin film is CH3NH3PbI3-xClxFilm.
8. the solar cell and LED of a kind of all-perovskite show the preparation method of integrated system, it is characterised in that including as follows Step：
A. the preparation of perovskite solar cell：
Transparent conducting glass substrate is cut, corroded and cleaned by I：
Transparent conducting glass substrate is cut into the fritter substrate of the shape and size with setting, then with zinc powder and mole dense Degree is not less than the width that 2M HCl solution erodes conductive layer setting on fritter substrate surface, then mole dense with what is diluted The region at least 60 seconds of being corroded of the HF acid soak fritter substrates for 2mol/L is spent, to ensure the region that is corroded of fritter substrate FTO layers of corrosion are clean, complete the patterned process to fritter substrate, and then progress Qula is logical successively washes by rubbing with the hands, then uses deionized water Rinse, ultrasound is then carried out using acetone or is cleaned by ultrasonic using ethanol, clean fritter substrate is then stored in second It is standby in alcohol；
The preparation of II window layer material titanium dioxide：
Molar concentration is not less than to 2M TiO2Precursor solution, is spin-coated under not higher than 2500rpm rotating speed by the step On the fritter substrate that rapid I corrosion cleaning is finished, TiO then will be coated2The fritter substrate of precursor solution carries out burned be cured to Few 10min, makes solidification on fritter substrate combine TiO2Material layer, then will carry TiO2The fritter substrate of material layer is transferred to horse Not in stove, in air atmosphere be not less than 500 DEG C anneal at least 30 minutes, titanium dioxide Window layer is prepared, then to dioxy The surface for changing titanium Window layer carries out TiCl4Processing, in titanium dioxide window layer surface one layer of tiny titanium dioxide dense of formation Crystal grain, as progress TiCl4During processing, first by TiCl4It is placed in refrigerator and is cooled to not higher than 4 DEG C, then in the condition being stirred continuously Under, a certain amount of TiCl is added dropwise into the deionized water in ice bath environment4, configuration concentration is not higher than 0.04mol/L's TiCl4The aqueous solution, is then placed in TiCl by the substrate with titanium dioxide Window layer of preparation4In the aqueous solution, it is heated to being not less than 70 DEG C keep being no less than 30min, and the substrate with titanium dioxide Window layer then is cleaned into drying, standby；
III single steps solution growth prepares CH3NH3PbI3-xClxPerovskite thin film：
Using spin-coating method by CH3NH3PbI3-xClxTwo kinds of precursor solutions be coated uniformly on what is prepared in the step II respectively In the titanium dioxide Window layer combined with substrate, calcium titanium ore bed is prepared, spin coating rotating speed is 1500~3000rpm, and spin-coating time is extremely It is less 60 seconds, it is after spin coating, wet calcium titanium ore bed is directly burned at a temperature of not higher than 100 DEG C at least 90 minutes, make calcium titanium The color of ore bed is all changed into sepia from yellow, and then the substrate with calcium titanium ore bed is dried at ambient temperature, Annealed again, that is, obtain the CH of grey black3NH3PbI3-xClxFilm；
The preparation of IV hole transport layer materials：
0.2292g spiro-MeOTAD powder is added in 1 milliliter of chlorobenzene, stirred at normal temperatures, after complete solubilization 34 microlitres of 4- tert .-butylpyridines are added dropwise, 0.1011g lithium salts are added in 500 microlitres of acetonitriles, stirring at normal temperature dissolves it, takes 100 microlitres of this uniform liquid dissolved are added in spiro-MeOTAD precursor solutions, continue to stir uniform to solution, The precursor solution that mass percent concentration is 16% is prepared, chlorobenzene is then added and this solution is diluted to the three of original concentration / mono-, the HTM precursor solutions of hole transmission layer needed for being, then to be not less than 2000rpm rotating speed, by this presoma Solution is spun on the calcium titanium ore bed prepared in the step III, you can obtain hole transport layer film, then condition of nitrogen gas Under, shading stands at least 24h；
V plated electrodes：
After the device shading prepared in the step IV is stood, 10 are not higher than in body vacuum-4Under conditions of Torr, pass through Vacuum evaporation technology, the gold that evaporation thickness is not higher than 200nm on hole transport layer film prepares to electrode and completes plane Type perovskite solar cell device；
B. the preparation of perovskite light-emitting diode display part：
(1) the preparation of ZnO nano particle：ZnO nano particle is synthesized using sol-gel process, comprised the following steps that：
1. 3mmol zinc acetate dihydrate is dissolved in 30mlDMSO solution；
2. 5mmol TMAH is dissolved in 30ml ethanol, and 1. gained is added dropwise to be not less than 8ml/min speed with syringe pump In solution, react lasting at room temperature and carry out being no less than 1h；
3. excessive toluene cleaning is added, and centrifugation separates out ZnO nano particle, and be dispersed in ethanol solution, obtain oxygen Change zinc ethanol solution, electron transport layer materials are used as spin coating；
(2) perovskite is synthesized：
By 1mmol MAI and 1mmol PbI2DMSO or mass fraction are dissolved in in 40wt.% DMF, in nitrogen environment, Not higher than 60 DEG C are heated and stirred at least 2 hours, obtain MAPbI3Solution；
(3) the preparation of Pe-LED devices：
(a) first wash glass substrate by rubbing with the hands with cleanser, be then cleaned by ultrasonic respectively with liquid detergent, deionized water, acetone, isopropanol respectively At least 30 minutes, then glass substrate is toasted at least 10 minutes, cathode substrate is used as；
(b) cathode substrate prepared in the step (a) is transferred in glove box, the atmosphere in control glove box makes O2It is dense Degree is not higher than 1PPM, and H2The concentration of O steam is also not higher than 1PPM, by the zinc oxide ethanol solution of the step (1) middle preparation Concentration be adjusted to 25mg/ml, then 25mg/ml zinc oxide ethanol solution is spin-coated to the rotating speed for being not less than 2000rpm In in cathode substrate, and annealed at least 30 minutes in nitrogen atmosphere with being not less than 150 DEG C within few 60 seconds, then naturally cool to room Temperature, i.e., prepare ZnO film in cathode substrate, is used as electron transfer layer；
(c) using the MAPbI prepared in the step (2)3On solution, the ZnO film surface prepared in the step (b), By MAPbI3Solution is annealed to being not less than 3000rpm rotating speed spin coating 40~60 seconds with the temperature for being not less than 80 DEG C It is few 10 minutes, i.e., MAPbI is prepared on ZnO film3Film, as luminescent layer, then with speckling with the swab stick of DMF solution by the moon The unnecessary ZnO film of pole substrate surrounding, MAPbI3Film is wiped, and so that the electrode for exposing cathode substrate draws angle, is obtained after finishing Substrate device；
(d) with not higher thanSpeed, evaporation thickness is not higher than what 60nm CBP materials were prepared in the step (c) MAPbI3On film, CBP films are prepared, hole transmission layer is used as；Then with not higher thanSpeed, CBP films it On, evaporation thickness is not higher than 10nm MoO3Material layer, prepares MoO3Film, is used as hole injection layer；
(e) electrode is steamed：Under vacuum conditions, the MoO prepared in the step (d)3On film, to be not less thanSpeed Degree evaporation thickness is not higher than 150nm Al electrodes, completes the preparation of light-emitting diode display part；
C. system is integrated：
By wire, by the anode of the perovskite solar cell device prepared in the step a with being made in the step b The negative electrode series connection of standby light-emitting diode display part, and by the cathode substrate of perovskite solar cell device and the light-emitting diode display part Anode substrate series connection, form closed-loop path, the perovskite solar cell device absorbs solar energy, and release electric energy and be Light-emitting diode display part is powered, and the solar cell and LED for obtaining all-perovskite show integrated system.
9. the solar cell of all-perovskite and LED show the preparation method of integrated system, its feature according to claim 8 It is：When preparing light-emitting diode display part in the step b, the step (3) the step of (c) prepare MAPbI3After film, connect And the substrate device prepared in the step (c) is transferred in multi-source gas-phase deposition system, control multi-source vapour deposition system The chamber pressure of system is 5x10-3Pa, the temperature of regulation correspondence evaporation source, makes TPBI materials reach sublimation point, and with gaseous deposit In MAPbI3On film, densification TPBI films are formed, as hole blocking layer, then in step (d), CBP materials are evaporated On the TPBI films prepared in the step (c), CBP films are prepared, hole transmission layer is used as.
CN201710082403.9A 2017-02-16 2017-02-16 The solar cell and LED of all-perovskite show integrated system and preparation method thereof Pending CN106981500A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110047998A (en) * 2018-01-17 2019-07-23 杭州纤纳光电科技有限公司 A kind of immersion prepares the equipment and application method of perovskite solar battery
CN113838981A (en) * 2021-09-15 2021-12-24 蜂巢能源科技(马鞍山)有限公司 Photoelectric energy storage device and preparation method thereof
CN113838887A (en) * 2021-08-31 2021-12-24 电子科技大学 Self-powered full perovskite light emitting diode

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CN201487785U (en) * 2009-03-25 2010-05-26 贾玉成 Solar street lamp
US20150053259A1 (en) * 2013-08-22 2015-02-26 Plant PV P-type doping of ii-vi materials with rapid vapor deposition using radical nitrogen
CN105470400A (en) * 2015-11-19 2016-04-06 华北电力大学 Perovskite film preparation method and application

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CN201487785U (en) * 2009-03-25 2010-05-26 贾玉成 Solar street lamp
US20150053259A1 (en) * 2013-08-22 2015-02-26 Plant PV P-type doping of ii-vi materials with rapid vapor deposition using radical nitrogen
CN105470400A (en) * 2015-11-19 2016-04-06 华北电力大学 Perovskite film preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110047998A (en) * 2018-01-17 2019-07-23 杭州纤纳光电科技有限公司 A kind of immersion prepares the equipment and application method of perovskite solar battery
CN110047998B (en) * 2018-01-17 2023-09-26 杭州纤纳光电科技有限公司 Device for preparing perovskite solar cell in immersion mode and use method
CN113838887A (en) * 2021-08-31 2021-12-24 电子科技大学 Self-powered full perovskite light emitting diode
CN113838887B (en) * 2021-08-31 2024-04-05 电子科技大学 Self-powered all-perovskite light-emitting diode
CN113838981A (en) * 2021-09-15 2021-12-24 蜂巢能源科技(马鞍山)有限公司 Photoelectric energy storage device and preparation method thereof

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Application publication date: 20170725